CN101993328B - Catalytic conversion combination method for producing propylene and high-quality fuel oil in high yield - Google Patents
Catalytic conversion combination method for producing propylene and high-quality fuel oil in high yield Download PDFInfo
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- CN101993328B CN101993328B CN200910169667.3A CN200910169667A CN101993328B CN 101993328 B CN101993328 B CN 101993328B CN 200910169667 A CN200910169667 A CN 200910169667A CN 101993328 B CN101993328 B CN 101993328B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a catalytic conversion combination method for producing propylene and high-quality fuel oil in high yield. Raw oil is contacted with a catalyst in a reactor so as to perform reaction. The method is characterized in that: the reaction temperature, the weight hourly space velocity and the weight ratio of the catalyst to the raw oil ensure that a reaction product containing catalytic wax which accounts for 12 to 60 weight percent of the raw oil is obtained through the reaction, wherein the weight hourly space velocity is 25 to 100 hour<-1>; the reaction temperature is 450 to 600 DEG C; the weight ratio of the catalyst to the raw oil is 1 to 30; and the catalytic wax is further treated by a hydrocracking process. In the method, the heavy raw oil is converted into high-octane gasoline and propylene, and the cetane number of the diesel is improved, so that yield of dry gas and coke is greatly reduced; therefore, the high-efficiency utilization of the oil resources is realized.
Description
Technical field
The present invention relates to a kind of catalytic conversion combination method, particularly when heavy feed stock is converted into stop bracket gasoline and propylene, improve diesel-fuel cetane number, thereby and make dry gas and coke yield significantly reduce the method for the efficient utilization that realizes petroleum resources.
Background technology
The low-carbon alkenes such as propylene are important Organic Chemicals, and propylene is the synthon of the products such as polypropylene, vinyl cyanide.Along with increasing rapidly of the derivative demands such as polypropylene, the demand of propylene is also all being increased year by year.The demand in World Propylene market 1,520 ten thousand tons from 20 years is increased to 5,120 ten thousand tons in 2000, and average growth rate per annum reaches 6.3%.The demand that expects propylene in 2010 will reach 8,600 ten thousand tons, and average growth rate per annum is about 5.6% therebetween.
The method of producing propylene is mainly steam cracking and catalytic cracking (FCC), wherein steam cracking be take the lightweight oils such as petroleum naphtha and by thermo-cracking, is produced ethene, propylene as raw material, but the productive rate of propylene is only 15 heavy % left and right, it is raw material that FCC be take the mink cell focuses such as vacuum gas oil (VGO).At present, 61% propylene is produced the byproduct of ethene from steam cracking in the world, 34% byproduct from refinery FCC production vapour, diesel oil, and a small amount of (approximately 5%) is obtained by dehydrogenating propane and ethene-butylene metathesis reaction.
If petrochemical complex is walked traditional preparing ethylene by steam cracking, propylene route, will face several large restraining factors such as the shortage of lightweight material oil, inefficiency of production and high cost.
FCC is because the advantages such as its adaptability to raw material is wide, flexible operation come into one's own day by day.In the U.S., almost 50% of propylene market demand all derive from FCC apparatus.It is very fast that the catalytic cracking of propylene enhancing improves technical development.
US4,980,053 disclose a kind of hydrocarbon conversion processes of preparing low-carbon olefins, and the petroleum fractions that raw material is different boiling ranges, residual oil or crude oil are used solid acid catalyst in fluidized-bed or moving-burden bed reactor, at 500～650 ℃ of temperature, pressure 1.5～3 * 10
5pa, weight hourly space velocity 0.2～2.0h
-1, agent-oil ratio 2～12 condition under carry out catalytic conversion reaction, reacted catalyzer Returning reactor internal recycle after coke burning regeneration is used.The overall yield of the method propylene and butylene can reach 40% left and right, and wherein productivity of propylene is up to 26.34%.
WO00/31215A1 discloses a kind of catalyst cracking method of producing alkene, and the method adopts ZSM-5 and/or ZSM-11 zeolite to do active ingredient, and the catalyzer that a large amount of inert substances of take are matrix, take VGO as raw material, and the productive rate of propylene is also no more than 20 heavy %.
US4,422,925 disclose the method that the multiple hydro carbons with different cracking performances contacts and transforms with hot regenerated catalyst, hydro carbons described in the method at least contains a kind of gas alkane raw material and a kind of liquid hydrocarbon raw material, the method has different cracking performances according to different hydrocarbon molecules, reaction zone is divided into a plurality of reaction zones and carries out cracking reaction, with voluminous low-molecular olefine.
Along with expanding economy, global gasoline car recoverable amount increases year by year, therefore the demand of premium-type gasoline is improved day by day.The technology that improves at present gasoline octane rating mainly contains catalytic reforming technology, alkylation techniques, isomerization technique and interpolation gasoline octane rating improving agent etc.The great advantage of catalytic reforming gasoline is that its heavy constituent octane value is higher, and light constituent octane value is lower.But reformation technology catalyzer cost is high and high to ingredient requirement.Alkylation techniques and isomerization technique obtain reformulated gasoline oil and have the advantages that octane value is high, susceptibility is good, are desirable clean gasoline with high octane components, but the catalyzer using all exists corrosion and environmental issue.The interpolation of the gasoline octane rating improving agents such as MTBE (methyl tertiary butyl ether) and ETBE (Ethyl Tertisry Butyl Ether) really can improve gasoline octane value, improve automotive performance, but cost is generally higher.Catalytically cracked gasoline is one of motor spirit main source, catalytically cracked gasoline last running part octane value is on the low side, thereby affect the octane value of gasoline, in addition, catalytic cracking diesel oil is second-rate, but catalytic cracking diesel oil contains more mononuclear aromatics, the mononuclear aromatics in diesel oil is converted into the increase that gasoline component had both been conducive to gasoline yield, can improve again octane value the energy propylene enhancing of gasoline simultaneously.
To alkane molecule, cracking reaction designs still Shortcomings to above-mentioned prior art, cause and increasing in productivity of propylene situation, dry gas yied increases considerably, simultaneously, prior art is underused the gasoline potential content in gasoline octane rating and diesel oil, cause productivity of propylene on the low side, there is room for improvement in gasoline yield and quality simultaneously.In order to meet growing low-carbon alkene industrial chemicals and the demand of motor spirit, CN101362959A discloses the catalysis conversion method of a kind of preparing propone and stop bracket gasoline, the raw material of difficult cracking first contacts with hot regenerated catalyst, at 600～750 ℃ of temperature, weight hourly space velocity 100～800h
-1, pressure 0.10～1.0MPa, catalyzer and raw material weight ratio 30～150, the weight ratio of water vapor and raw material is to carry out cracking reaction under 0.05～1.0 condition, reactant flow is mixed with the stock oil of easily cracking, at 450～620 ℃ of temperature, weight hourly space velocity 0.1～100h
-1, pressure 0.10～1.0MPa, catalyzer and raw material weight ratio 1.0～30, under the condition that the weight ratio of water vapor and raw material is 0.05～1.0, carry out cracking reaction; After reclaimable catalyst is separated with reaction oil gas, reclaimable catalyst enters stripper, Returning reactor after stripping, coke burning regeneration, reaction oil gas is isolated to object product propylene and stop bracket gasoline and the raw material of cracking again, and cut, heavy aromatics that the raw material packet of described cracking is again 180～260 ℃ containing boiling range are raffinated oil.Productive rate and the selectivity of the method propylene significantly increase, and productive rate and the octane value of gasoline improve significantly, and dry gas yied reduces amplitude up to more than 80 heavy %, but diesel cetane-number is relatively low.
Summary of the invention
Technical problem to be solved by this invention is that a kind of catalytic conversion combination method is provided on the basis of existing technology, particularly when heavy feed stock is converted into stop bracket gasoline and propylene, improve diesel-fuel cetane number, thereby and dry gas and coke yield are significantly reduced realize the efficient utilization of petroleum resources.
Technical scheme of the present invention is the catalytic conversion combination method of a kind of producing more propylene and high-grade fuel oil, and the method comprises the following steps:
Stock oil contacts and reacts with catalyzer in reactor, it is characterized in that temperature of reaction, weight hourly space velocity, catalyzer are enough to make to react obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil with stock oil weight ratio, wherein said weight hourly space velocity is 25～100h
-1described temperature of reaction is 450～600 ℃, described catalyzer and stock oil weight ratio are 1～30, catalytic wax oil enters catalytic wax oil hydroeracking unit and further processes, and the catalytic wax oil hydrocracking tail oil that hydrocracking obtains is as the raw material of one or more equipment in voluminous gasoline apparatus, this reactor, hydroeracking unit, steam cracking device, other reactor.
In a more preferred embodiment, temperature of reaction is 450～600 ℃, preferably, and 460～580 ℃, more preferably, 480～540 ℃.
In a more preferred embodiment, weight hourly space velocity is 30～80h
-1, preferably, 40～60h
-1.
In a more preferred embodiment, catalyzer and stock oil weight ratio are 1～30, preferably, and 2～25, more preferably, 3～14.
In a more preferred embodiment, reaction pressure is 0.10MPa～1.0MPa.
In a more preferred embodiment, described stock oil is selected from or comprises petroleum hydrocarbon and/or other mineral oil, its Petroleum Hydrocarbon is selected from one or more the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, shale oil.
In a more preferred embodiment, described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for respectively total catalyst weight: the heavy % of zeolite 1～50, the heavy % of inorganic oxide 5～99, the heavy % of clay 0～70, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51～100 heavy % of zeolite gross weight, preferably the 70 heavy % in heavy %～100.Large pore zeolite accounts for 0～49 heavy % of zeolite gross weight, preferably 0～30 heavy %.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from Y-series zeolite.
In a more preferred embodiment, described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or the two or more combinations of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
In a more preferred embodiment, a position, described stock oil is introduced in reactor, or in the position of more than one identical or different height, described stock oil is introduced in reactor.
In a more preferred embodiment, described method also comprises carries out reaction product and catalyzer separated, and catalyzer is Returning reactor after stripping, coke burning regeneration, and the product after separation comprises propylene, stop bracket gasoline and catalytic wax oil.
In a more preferred embodiment, described catalytic wax oil is that initial boiling point is not less than the cut of 260 ℃, and hydrogen richness is not less than 10.5 heavy %.
In a more preferred embodiment, described catalytic wax oil is that initial boiling point is not less than the cut of 330 ℃, and hydrogen richness is not less than 10.8 heavy %.
The reactive system of hydroeracking unit generally includes refining reaction device and cracking case, be fixed-bed reactor, refining reaction device loads hydrotreating catalyst conventionally, this hydrotreating catalyst be load on unformed aluminum oxide or/and the group vib in silica-alumina supports or/and VIII family non-precious metal catalyst; Hydrocracking catalyst is to load on group vib on y-type zeolite molecular sieve or/and VIII family non-precious metal catalyst.Wherein said group vib base metal is molybdenum or/and tungsten, and VIII family base metal is one or more in nickel, cobalt, iron.
The processing condition of described hydrocracking are: hydrogen dividing potential drop 4.0～20.0MPa, 280～450 ℃ of temperature of reaction, volume space velocity 0.1～20h
-1, hydrogen-oil ratio 300～2000v/v.Hydrogen-oil ratio in the present invention all refers to the volume ratio of hydrogen and catalytic wax oil.
In another embodiment of the invention, provide a kind of catalytic conversion combination method, wherein stock oil contacts and reacts with catalyzer in reactor, it is characterized in that
(1) stock oil comprises cracking stock oil and cracking stock oil again, a position, described stock oil is introduced in reactor, or in the position of more than one identical or different height, described stock oil is introduced in reactor;
(2) cracking stock oil is not later than cracking stock oil and reacts in reactor again;
(3) temperature of reaction, weight hourly space velocity, catalyzer are enough to make to react obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil with stock oil weight ratio;
(4) the described weight hourly space velocity of cracking stock oil is 5～100h
-1;
(5) catalytic wax oil enters catalytic wax oil hydroeracking unit;
(6) the catalytic wax oil hydrocracking tail oil that hydrocracking obtains is as the raw material of one or more equipment in voluminous gasoline apparatus, this reactor, hydroeracking unit, steam cracking device, other reactor.
In a more preferred embodiment, the grease separation of described cracking stock again from or comprise one or more the mixture in the hydrocarbon that slurry oil cut, diesel oil distillate, gasoline fraction, carbonatoms are 4～8.
In a more preferred embodiment, described cracking stock grease separation from or comprise petroleum hydrocarbon and/or other mineral oil, its Petroleum Hydrocarbon is selected from one or more the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, shale oil.
In a more preferred embodiment, it is the cut of 180～260 ℃ that reaction oil gas also can obtain boiling range through separation, this cut as cracking stock oil again or/and cracking stock oil turns back to this reactor reacts.Described boiling range scope is that the cut of 180～260 ℃ can, from catalytic cracking method of the present invention, also can, from techniques such as conventional catalytic cracking, coking, thermally splitting and hydrogenation, comprise any cut that is rich in mononuclear aromatics simultaneously.
In a more preferred embodiment, described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for respectively total catalyst weight: the heavy % of zeolite 1～50, the heavy % of inorganic oxide 5～99, the heavy % of clay 0～70, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51～100 heavy % of zeolite gross weight, preferably the 70 heavy % in heavy %～100.Large pore zeolite accounts for 0～49 heavy % of zeolite gross weight, and mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from Y-series zeolite.
In a more preferred embodiment, described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or the two or more combinations of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
In a more preferred embodiment, then the reaction conditions of cracking stock oil be: 600～750 ℃ of temperature of reaction, weight hourly space velocity 100～800h
-1, reaction pressure 0.10～1.0MPa, catalyzer and the weight ratio 30～150 of cracking stock oil again, water vapor is 0.05～1.0 with the weight ratio of cracking stock oil again.
In a more preferred embodiment, the reaction conditions of cracking stock oil is: 450～600 ℃ of temperature of reaction, weight hourly space velocity 5～100h
-1, reaction pressure 0.10～1.0MPa, catalyzer and cracking stock oil weight ratio 1.0～30, the weight ratio of water vapor and cracking stock oil is 0.05～1.0.
In a more preferred embodiment, the temperature of reaction of cracking stock oil is 460～580 ℃, and weight hourly space velocity is 10～90h
-1, be preferably 20～60h
-1, 30～50h more preferably
-1, catalyzer and stock oil weight ratio are 3～14.
In a more preferred embodiment, described method also comprises carries out reaction product and catalyzer separated, and catalyzer is Returning reactor after stripping, coke burning regeneration, and the product after separation comprises propylene, stop bracket gasoline and catalytic wax oil.
In a more preferred embodiment, described catalytic wax oil is that initial boiling point is not less than the cut of 260 ℃, and hydrogen richness is not less than 10.5 heavy %.
In a more preferred embodiment, described catalytic wax oil is that initial boiling point is not less than the cut of 330 ℃, and hydrogen richness is not less than 10.8 heavy %.
In a more preferred embodiment, described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or the two or more combinations of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.Wherein the gas speed of fluidized-bed is 0.1 meter per second～2 meter per second, and the gas speed of riser tube is 2 meter per second～30 meter per seconds (disregarding catalyzer).
Preferred forms of the present invention is to carry out in a kind of reducing riser reactor, about the more detailed description of this reactor referring to CN1237477A.
In order to increase the agent-oil ratio of reaction catchment, improve the catalytic activity of catalyzer, can be by supplemental heat or cold regenerated catalyst, half regenerated catalyst, catalyzer, live catalyst to be generated.Cooling regenerated catalyst and half cooling regenerated catalyst are reclaimable catalyst cooling obtaining after two-stage regeneration and one section of regeneration respectively, regenerated catalyst carbon content is below 0.1 heavy %, be preferably below 0.05 heavy %, half regenerated catalyst carbon content is the 0.1 heavy % in heavy %～0.9, and preferably carbon content is the 0.15 heavy % in heavy %～0.7; Reclaimable catalyst carbon content is more than 0.9 heavy %, and preferably carbon content is the 0.9 heavy % in heavy %～1.2.
The method that the method such as separation of propylene is known with those of ordinary skills from reaction product is identical; The separated described cut of 180～260 ℃, preferably the cut of 190～250 ℃ can in existing FCC separation column, carry out separation also can be separated in separation column separately; Or be greater than the cut (or being greater than the cut of 330 ℃) of 250 ℃ or 260 ℃ as the stock oil of catalytic cracking unit, or the catalytic wax oil (or being greater than the catalytic wax oil of 330 ℃) that is greater than 250 ℃ or 260 ℃ adopts hydrocracking mode to process.
The reactive system of hydroeracking unit generally includes refining reaction device and cracking case, be fixed-bed reactor, refining reaction device loads hydrotreating catalyst conventionally, this hydrotreating catalyst be load on unformed aluminum oxide or/and the group vib in silica-alumina supports or/and VIII family non-precious metal catalyst; Hydrocracking catalyst is to load on group vib on y-type zeolite molecular sieve or/and VIII family non-precious metal catalyst.Wherein said group vib base metal is molybdenum or/and tungsten, and VIII family base metal is one or more in nickel, cobalt, iron.
The processing condition of described hydrocracking are: hydrogen dividing potential drop 4.0～20.0MPa, 280～450 ℃ of temperature of reaction, volume space velocity 0.1～20h
-1, hydrogen-oil ratio 300～2000v/v.
This technical scheme organically combines the techniques such as catalytic pyrolysis and catalytic wax oil hydrocracking, produces to greatest extent especially propylene of stop bracket gasoline, low-carbon alkene, and improve diesel cetane-number from the lower heavy feed stock of hydrogen richness.The present invention compared with prior art, has following technique effect:
1, productivity of propylene and the propylene selectivity in liquefied gas increases considerably; Gasoline yield increases significantly, and gasoline octane rating improves significantly; Diesel cetane-number improves.
2,, in the situation that productivity of propylene increases considerably, dry gas yied and coke reduce significantly.
3, yield of light oil increases significantly, and slurry oil productive rate reduces significantly, thereby petroleum resources utilising efficiency improves.
Accompanying drawing explanation
Accompanying drawing is process flow diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further detailed, but does not therefore limit the present invention.
Accompanying drawing is process flow diagram of the present invention.
Its technical process is as follows:
Pre-lift medium is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 16 under the castering action of pre-lift medium along the riser tube accelerated motion that makes progress, again cracking stock oil through pipeline 3 bottom with injecting lift pipe 2 reaction zone I together with atomizing steam from pipeline 4, mix with the existing logistics of riser reactor, there is cracking reaction in cracking stock again on hot catalyzer, and upwards accelerated motion.Cracking stock oil is the middle and lower part with injecting lift pipe 2 reaction zone I together with atomizing steam from pipeline 6 through pipeline 5, mix with the existing logistics of riser reactor, on the lower catalyzer that contains certain charcoal, there is cracking reaction in cracking stock, and upwards accelerated motion enters reaction zone II continuation reaction, the oil gas generating and the reclaimable catalyst of inactivation enter the cyclonic separator in settling vessel 8 through pipeline 7, realize the separated of reclaimable catalyst and oil gas, oil gas enters collection chamber 9, and catalyst fines returns to settling vessel 8 by dipleg.Reclaimable catalyst in settling vessel 8 flows to stripping stage 10, contacts with the steam from pipeline 11.The oil gas going out from stripping reclaimable catalyst enters collection chamber 9 after cyclonic separator separation.Reclaimable catalyst after stripping enters revivifier 13 through inclined tube 12, and main air enters revivifier 13 through pipeline 14, and the coke on burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters cigarette machine through pipeline 15.Catalyzer after regeneration enters riser reactor 2 through inclined tube 16.
Oil gas in collection chamber 9, through main oil gas piping 17, enters follow-up separation system 18, and the propylene that separation obtains is drawn through pipeline 19, and the propane that separation obtains is drawn through pipeline 28; And carbon four hydrocarbon are drawn through pipeline 20, also can return to riser tube 2; Catalytic pyrolysis dry gas is drawn through pipeline 21; Catalytic cracking gasoline is drawn through pipeline 27, and preferred boiling range is less than 65～110 ℃ of gasoline fractions and draws as cracking stock again and return to riser reactor 2 through pipeline 22; Diesel oil distillate is drawn through pipeline 29; Catalytic wax oil enters hydrocracking unit 24 through pipeline 23, and isolated hydrocracking product is further separated through pipeline 25, and hydrocracking tail oil is sent into this reactor (being riser reactor 2) or/and voluminous gasoline apparatus 27 through pipeline 26.The oil gas that fecund gasoline apparatus generates can enter fractionating system 18 through gas pipeline 28 and carry out separation or/and enter other fractionating system.Wherein each cut boiling range regulates according to refinery's actual needs.
The following examples will be further described present method, but therefore not limit present method.
In embodiment, raw material used is vacuum gas oil (VGO), and its character is as shown in table 1.
Catalytic cracking catalyst preparation method used in embodiment is summarized as follows:
1), by 20gNH
4cl is dissolved in 1000g water, in this solution, adds 100g (butt) crystallization product ZRP-1 zeolite (Qilu Petrochemical Company's catalyst plant production, SiO
2/ Al
2o
3=30, content of rare earth RE
2o
3=2.0 heavy %), after 90 ℃ of exchange 0.5h, filter to obtain filter cake; Add 4.0gH
3pO
4(concentration 85%) and 4.5gFe (NO
3)
3be dissolved in 90g water, dry with filter cake hybrid infusion; Then at 550 ℃ of roasting temperatures, process and within 2 hours, obtain phosphorous and MFI structure mesopore zeolite iron, its elementary analytical chemistry consists of
0.1Na
2O·5.1Al
2O
3·2.4P
2O
5·1.5Fe
2O
3·3.8RE
2O
3·88.1SiO
2。
2), use 250kg decationized Y sieve water by 75.4kg halloysite (Suzhou china clay company Industrial products, solid content 71.6m%) making beating, add again 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63m%), with hydrochloric acid, its PH is adjusted to 2～4, stir, at 60～70 ℃ standing aging 1 hour, keeping PH was 2～4, cools the temperature to below 60 ℃, add 41.5Kg aluminium colloidal sol (Qilu Petrochemical Company's catalyst plant product, Al
2o
3content is 21.7m%), stir 40 minutes, obtain mixed serum.
3), by step 1) MFI structure mesopore zeolite (butt is 22.5kg) and DASY zeolite (Qilu Petrochemical Company's catalyst plant Industrial products of the phosphorous and iron prepared, lattice constant is 2.445～2.448nm, butt is 2.0kg) join step 2) in the mixed serum that obtains, stir, spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1m%) washing, wash away free Na
+, being drying to obtain catalytic cracking catalyst sample, consist of 18 heavy % MFI structure mesopore zeolite, 2 heavy %DASY zeolites, the 28 heavy % pseudo-boehmites, 7 phosphorous and iron of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.
In embodiment, Hydrobon catalyst used and the trade names of hydrocracking catalyst are respectively RN-2 and RT-1, by Sinopec catalyzer branch office Chang Ling catalyst plant, produce.
Embodiment 1
This embodiment tests according to the flow process of accompanying drawing, stock oil A is directly as the stock oil of catalytic pyrolysis, on the middle-scale device by riser reactor, test, cracking stock oil enters I middle and upper part, reaction zone, butylene enters reaction zone I bottom as cracking stock oil again, in reaction zone I bottom, then cracking stock oil is at 630 ℃ of temperature of reaction, weight hourly space velocity 180h
-1, catalytic cracking catalyst and the again weight ratio 62 of cracking stock oil, water vapor and the again weight ratio of cracking stock oil are under 0.20 condition, to carry out cracking reaction; In I middle and upper part, reaction zone, cracking stock oil is at 575 ℃ of temperature of reaction, weight hourly space velocity 65h
-1the weight ratio 10 of catalytic cracking catalyst and cracking stock oil, the weight ratio of water vapor and cracking stock oil is under 0.15 condition, to carry out cracking reaction, in addition, from stripping stage, supplement the steam stripped reclaimable catalyst of part and enter reaction zone II bottom, to reduce temperature and the reaction weight hourly space velocity of reaction zone II.At reaction zone II, oil gas is at 530 ℃ of temperature of reaction, weight hourly space velocity 20h
-1the weight ratio of water vapor and cracking stock oil is under 0.15 condition, to carry out cracking reaction, oil gas is separated at settling vessel with the catalyzer for the treatment of charcoal, product cuts by boiling range in separation system, thereby obtain propylene and gasoline, the catalytic wax oil that part carbon four hydrocarbon, boiling range > are 260 ℃.Catalytic wax oil is delivered to hydroeracking unit and is processed, and the reactive system of this hydroeracking unit comprises refining reaction device and two reactors of cracking case, at hydrogen dividing potential drop 12.0/11.5MPa, 375/371 ℃ of temperature of reaction, volume space velocity 0.90/1.1h
-1reaction conditions under carry out hydrotreatment, the hydrocracking tail oil after hydrogenation returns to I middle and upper part, this riser reactor reaction zone.Operational condition and product distribute and list in table 2.
As can be seen from Table 2, productivity of propylene is up to 14.96 heavy %, and gasoline yield is 37.05 heavy %, and rocket engine fuel productive rate is 13.56 heavy %.The octane value of gasoline (RON) is 93.5, and diesel-fuel cetane number is 41.0.
Table 1
| Stock oil numbering | A |
| Stock oil character | |
| Density (20 ℃), g/cm 3 | 0.8997 |
| Sulphur content, ppm | 2000 |
| Nitrogen content, ppm | 1500 |
| Aromatic hydrocarbons, heavy % | 23.4 |
| C, heavy % | 86.61 |
| H, heavy % | 12.73 |
| Boiling range (ASTM D-1160), ℃ | |
| IBP | 283 |
| 10％ | 376 |
| 30％ | 410 |
| 50％ | 433 |
| 70％ | 460 |
| 90％ | 511 |
| 95％ | 523 |
| EP | 541 |
Table 2
| Embodiment 1 | |
| Stock oil numbering | A |
| Catalytic pyrolysis unit | |
| Operational condition | |
| Outlet temperature of riser, ℃ | 515 |
| Riser reaction zone II | |
| Temperature of reaction, ℃ | 530 |
| Weight hourly space velocity, h -1 | 20 |
| The weight ratio of water vapor/stock oil | 0.15 |
| Riser reaction zone I | |
| Medial temperature, ℃ | 630/575 |
| Agent-oil ratio, m/m | 62/10 |
| Weight hourly space velocity, h -1 | 180/60 |
| The weight ratio of water vapor/stock oil | 0.20/0.15 |
| Hydrocracking unit | |
| Hydrogen dividing potential drop, MPa | 12.0/11.5 |
| Temperature of reaction, ℃ | 375/371 |
| Volume space velocity, h -1 | 0.90/1.10 |
| Hydrogen-oil ratio, v/v | 705/900 |
| Product distributes, m% | |
| Dry gas | 3.37 |
| Liquefied gas | 31.96 |
| Propylene | 14.95 |
| Gasoline | 37.05 |
| Rocket engine fuel | 13.56 |
| Diesel oil | 8.85 |
| Coke | 5.42 |
| Loss | 0.50 |
| Add up to | 100.71 |
| Gasoline RON | 93.5 |
| Diesel cetane-number | 41.0 |
Claims (25)
1. the catalytic conversion combination method of a producing more propylene and high-grade fuel oil, wherein stock oil contacts and reacts with catalyzer in reactor, it is characterized in that temperature of reaction, weight hourly space velocity, catalyzer are enough to make to react obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil with stock oil weight ratio, wherein said weight hourly space velocity is 25～100h
-1described temperature of reaction is 450～600 ℃, described catalyzer and stock oil weight ratio are 1～30, catalytic wax oil enters catalytic wax oil hydroeracking unit and further processes, and the catalytic wax oil hydrocracking tail oil that hydrocracking obtains is as the raw material of one or more equipment in voluminous gasoline apparatus, this reactor, hydroeracking unit, steam cracking device; Described catalytic wax oil is the cut that initial boiling point is greater than 260 ℃, and hydrogen richness is not less than 10.5 heavy %.
2. according to the method for claim 1, it is characterized in that described stock oil is heavy petroleum hydrocarbon and/or other mineral oil, wherein heavy petroleum hydrocarbon is selected from one or more in vacuum residuum, long residuum inferior, hydrogenated residue inferior, coker gas oil, deasphalted oil, crude oil with high acid value, high metal crude oil; Other mineral oil is one or more in liquefied coal coil, tar sand oil, shale oil.
3. according to the method for claim 1, it is characterized in that described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for respectively total catalyst weight: the heavy % in heavy %～50 of zeolite 1, the heavy % in heavy %～99 of inorganic oxide 5, the heavy % in heavy %～70 of clay 0, its mesolite is as active ingredient, for mesopore zeolite and/or optional large pore zeolite, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, large pore zeolite selects free Rare Earth Y, rare earth hydrogen Y, the super steady Y that different methods obtains, the mixture of more than one in this group zeolite that high silicon Y forms.
4. according to the method for claim 1, it is characterized in that described reactor be selected from riser tube, etc. more than one the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or the plural combination of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
5. according to the method for claim 1, it is characterized in that a position, described stock oil being introduced in reactor, or in the position of more than one identical or different height, described stock oil is introduced in reactor.
6. according to the method for claim 1, it is characterized in that temperature of reaction is 460～580 ℃, weight hourly space velocity is 30～80h
-1, catalyzer and stock oil weight ratio be 2～25.
7. according to the method for claim 1, it is characterized in that temperature of reaction is 480～540 ℃.
8. according to the method for claim 1, it is characterized in that weight hourly space velocity is 40～60h
-1.
9. according to the method for claim 1, it is characterized in that catalyzer and stock oil weight ratio are 3～14.
10. according to the method for claim 1, it is characterized in that described reaction is to carry out under 0.10MPa～1.0MPa at pressure.
11. according to the method for claim 1, it is characterized in that described method also comprises reaction product and catalyzer to be carried out separated, and catalyzer is Returning reactor after stripping, coke burning regeneration, and the product after separation comprises propylene, stop bracket gasoline and catalytic wax oil.
12. according to the method for claim 10, it is characterized in that described catalytic wax oil is that initial boiling point is not less than the cut of 330 ℃, and hydrogen richness is not less than 10.8 heavy %.
13. according to the method for claim 1, it is characterized in that hydrocracking catalyst is to load on group vib on y-type zeolite molecular sieve or/and VIII family non-precious metal catalyst, wherein said group vib base metal is molybdenum or/and tungsten, and VIII family base metal is one or more in nickel, cobalt, iron.
14. according to the method for claim 1, it is characterized in that the processing condition of hydrocracking are: hydrogen dividing potential drop 4.0～20.0MPa, 280～450 ℃ of temperature of reaction, volume space velocity 0.1～20h
-1, hydrogen-oil ratio 300～2000v/v.
15. 1 kinds of catalysis conversion methods, wherein stock oil contacts and reacts with catalyzer in reactor, it is characterized in that
(1) stock oil comprises cracking stock oil and cracking stock oil again, a position, described stock oil is introduced in reactor, or in the position of more than two identical or different height, described stock oil is introduced in reactor to the mixture of more than one in the hydrocarbon that the grease separation of described cracking stock is again 4～8 from slurry oil, diesel oil, gasoline, carbonatoms;
(2) cracking stock oil is not later than cracking stock oil and reacts in reactor again, then the reaction conditions of cracking stock oil is: 600～750 ℃ of temperature of reaction, weight hourly space velocity 100～800h
-1, reaction pressure 0.10～1.0MPa, catalyzer and the weight ratio 30～150 of cracking stock oil again, water vapor is 0.05～1.0 with the weight ratio of cracking stock oil again;
(3) temperature of reaction, weight hourly space velocity, catalyzer are enough to make to react obtain comprising the reaction product that accounts for cracking stock oil 12～60 heavy % catalytic wax oil with the weight ratio of stock oil, described catalytic wax oil is that initial boiling point is not less than the cut of 260 ℃, and hydrogen richness is not less than 10.5 heavy %;
(4) reaction conditions of cracking stock oil is: 450～600 ℃ of temperature of reaction, weight hourly space velocity 5～100h
-1, reaction pressure 0.10～1.0MPa, catalyzer and cracking stock oil weight ratio 1.0～30, the weight ratio of water vapor and cracking stock oil is 0.05～1.0;
(5) catalytic wax oil enters catalytic wax oil hydroeracking unit;
(6) the catalytic wax oil hydrocracking tail oil that hydrocracking obtains is as the raw material of one or more equipment in voluminous gasoline apparatus, this reactor, hydroeracking unit, steam cracking device.
16. according to the method for claim 15, it is characterized in that described cracking stock grease separation is from petroleum hydrocarbon and/or other mineral oil, its Petroleum Hydrocarbon is selected from more than one the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum, and other mineral oil is more than one the mixture in liquefied coal coil, tar sand oil, shale oil.
17. according to the method for claim 15, it is characterized in that described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for respectively total catalyst weight: the heavy % of zeolite 1～50, the heavy % of inorganic oxide 5～99, the heavy % of clay 0～70, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51～100 heavy % of zeolite gross weight, large pore zeolite accounts for 0～49 heavy % of zeolite gross weight, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from Y-series zeolite.
18. according to the method for claim 15, it is characterized in that described reactor be selected from riser tube, etc. more than one the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or the plural combination of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
19. according to the method for claim 15, and the temperature of reaction that it is characterized in that described cracking stock oil is 460～580 ℃.
20. according to the method for claim 15, and the weight hourly space velocity that it is characterized in that described cracking stock oil is 10～90h
-1.
21. according to the method for claim 15, it is characterized in that catalyzer and described cracking stock weight of oil ratio are 3～14.
22. according to the method for claim 15, it is characterized in that described method also comprises reaction product and catalyzer to be carried out separated, and catalyzer is Returning reactor after stripping, coke burning regeneration, and the product after separation comprises propylene, stop bracket gasoline and catalytic wax oil.
23. according to the method for claim 15, it is characterized in that described catalytic wax oil is that initial boiling point is not less than the cut of 330 ℃, and hydrogen richness is not less than 10.8 heavy %.
24. according to the method for claim 15, it is characterized in that hydrocracking catalyst is to load on group vib on y-type zeolite molecular sieve or/and VIII family non-precious metal catalyst, wherein said group vib base metal is molybdenum or/and tungsten, and VIII family base metal is one or more in nickel, cobalt, iron.
25. according to the method for claim 15, it is characterized in that the processing condition of hydrocracking are: hydrogen dividing potential drop 4.0～20.0MPa, 280～450 ℃ of temperature of reaction, volume space velocity 0.1～20h
-1, hydrogen-oil ratio 300～2000v/v.
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| CN1796494A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Method for cracking hydrocarbon oil |
| CN101362963A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing aromatic hydrocarbons and light olefins |
| CN101362959A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing propone and high-octane number gasoline |
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| CN1796494A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Method for cracking hydrocarbon oil |
| CN101362963A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing aromatic hydrocarbons and light olefins |
| CN101362959A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing propone and high-octane number gasoline |
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